Core/shell polymer toughener suspended in epoxy resin

• US 6,111,015 A
• Filed: 02/21/1995
• Issued: 08/29/2000
• Est. Priority Date: 07/09/1992
• Status: Expired due to Term

• Current Assignee: Huntsman Advanced Materials Americas, Inc.
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Setiabudi, Frans, Peyer, Robert Peter, Eldin, Sameer H., Gruber, Urs
• Primary Examiner(s): Sellers, Robert E.
• Application Number:
  US08/391,329
• Time in Patent Office: 2,016 Days
• Field of Search: 525/65, 523/436
• US Class Current: 525/65
• CPC Class Codes: B32B 2260/023 Two or more layers
• CPC Class Codes: B32B 2260/046 Synthetic resin
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2315/085 Glass fiber cloth or fabric
• CPC Class Codes: B32B 5/02 characterised by structural features of a fibrous or filamentary layer layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02
• CPC Class Codes: B32B 5/26 another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: C08G 59/184 with amines
• CPC Class Codes: C08G 59/42 Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• CPC Class Codes: C08G 59/50 Amines
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 51/00 Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/04 grafted on to rubbers
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C09J 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: C09J 151/04 grafted on to rubbers

Abstract

Curable suspensions of an epoxy resin formulation comprising

a) a storage-stable suspension of an epoxy resin and a toughener suspended therein which contains no groups that react with a curable epoxy resin system,

b) dicyandiamide, a polycarboxylic acid, a polycarboxylic anhydride, a polyamine, a polyaminoamide, an amino group-containing adduct of an amine and a polyepoxide, a polyol or a catalytically curing hardener, and, as optional components,

c) a curing catalyst, conventional fillers or reinforcing materials,

are particularly suitable for use as casting resins, laminating resins or adhesives.

Claims

1. A curable suspension of an epoxy resin formulation consisting of

a) a storage-stable suspension of an epoxy resin and as toughener a core/shell polymer suspended therein in which the toughener is homogeneously dispersed in the form of very fine particles in the submicron range and wherein the core of the core/shell polymer consists of polybutadiene or butadiene/styrene copolymers and the shell contains no groups that react with a curable epoxy resin formulation, wherein said storage-stable suspension is prepared by either 1) when using liquid epoxy resins, adding the aqueous emulsion of a core/shell polymer, with or without a solvent, to the epoxy resin, and removing the water or mixture of water and solvent by vacuum distillation, or 2) when using solid epoxy resins, fusing the solid epoxy resin or dissolving it in a suitable solvent and adding the aqueous emulsion of a core/shell polymer to the epoxy resin, and subsequently removing the water or mixture of water and solvent by vacuum distillation;

b) as a curing agent a compound selected from the group consisting of dicyandiamide, a polycarboxylic acid;

a polycarboxylic anhydride;

a polyamine selected from the group consisting of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N,N-diethylethylenediamine, hexamethylenediamine, diethylenetriamine, triethylentetramine, tetraethylenepentamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, ethanolamine, m- and p-phenylenediamine, bis(4-aminophenyl)methane, aniline-formaldehyde resins, bis(4-aminophenyl)sulfone, m-xylylenediamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-amino-3-methylcyclohexyl)propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), and N-(2-aminoethyl)piperazine;

a polyaminoamide;

an amino group-containing adduct of an amine and a polyepoxide;

a polyol and a catalytic hardener, and, as optionally, at least one component selected from the group consisting of a curing accelerator, a reinforcing material, and a filler other than the reinforcing material.

2. A suspension according to claim 1, wherein the epoxy resin is a liquid or solid polyglycidyl ether or ester, or a cycloaliphatic epoxy resin.

3. Suspension according to claim 1, wherein the epoxy resin is a liquid or solid diglycidyl ether of a bisphenol, or a diglycidyl ester of a cycloaliphatic or aromatic dicarboxylic acid.

4. A suspension according to claim 1, wherein the curing agent is selected from the group consisting of a polycarboxylic acid, a polycarboxylic anhydride, 3,3'"'"'-dimethyl-4,4'"'"'-diaminodicyclohexylmethane, dicyandiamide and a catalytic hardener.

5. A suspension according to claim 1, wherein the curing agent is selected from the group consisting of 3,3'"'"'-dimethyl-4,4'"'"'diaminocyclohexylmethane, dicyandiamide and a catalytic hardener.

7. A casting resin, a laminating resin or an adhesive comprising a suspension as claimed in claim 1 or 4.

6. A curable suspension of an epoxy resin formulation consisting of

a) a storage-stable suspension of an epoxy resin and as toughener a core/shell polymer suspended therein in which the toughener is homogeneously dispersed in the form of very fine particles in the submicron range and wherein the core of the core/shell polymer consists of polybutadiene or butadiene/styrene copolymers and the shell contains no groups that react with a curable epoxy resin formulation, wherein said storage-stable suspension is prepared by either 1) when using liquid epoxy resins, adding the aqueous emulsion of a core/shell polymer, with or without a solvent, to the epoxy resin, and removing the water or mixture of water and solvent by vacuum distillation, or 2) when using solid epoxy resins, fusing the solid epoxy resin or dissolving it in a suitable solvent and adding the aqueous emulsion of a core/shell polymer to the epoxy resin, and subsequently removing the water or mixture of water and solvent by vacuum distillation;

b) 3,3'"'"'-dimethyl-4,4'"'"'-diaminodicyclohexylmethane as a curing agent, and, as optionally, at least one component selected from the group consisting of a curing accelerator, a reinforcing material, and a filler other than the reinforcing material.